CN107257784B - For extracting C from aqueous streams1To C4Quaternary carboxylate compositions of carboxylic acids - Google Patents
For extracting C from aqueous streams1To C4Quaternary carboxylate compositions of carboxylic acids Download PDFInfo
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- CN107257784B CN107257784B CN201580076522.2A CN201580076522A CN107257784B CN 107257784 B CN107257784 B CN 107257784B CN 201580076522 A CN201580076522 A CN 201580076522A CN 107257784 B CN107257784 B CN 107257784B
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- Prior art keywords
- acid
- extraction
- solvent
- organic solvent
- water
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- 239000000203 mixture Substances 0.000 title claims abstract description 125
- 150000001735 carboxylic acids Chemical group 0.000 title claims abstract description 34
- 150000007942 carboxylates Chemical group 0.000 title description 19
- 238000000605 extraction Methods 0.000 claims abstract description 178
- 239000002253 acid Substances 0.000 claims abstract description 168
- 239000002904 solvent Substances 0.000 claims abstract description 164
- -1 tetraalkylphosphonium cations Chemical class 0.000 claims abstract description 70
- 238000000034 method Methods 0.000 claims abstract description 53
- 239000003960 organic solvent Substances 0.000 claims abstract description 29
- 150000007513 acids Chemical class 0.000 claims abstract description 26
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 346
- 235000011054 acetic acid Nutrition 0.000 claims description 104
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 104
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 58
- 125000004432 carbon atom Chemical group C* 0.000 claims description 45
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 40
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 claims description 32
- 230000002209 hydrophobic effect Effects 0.000 claims description 29
- KQNPFQTWMSNSAP-UHFFFAOYSA-N isobutyric acid Chemical compound CC(C)C(O)=O KQNPFQTWMSNSAP-UHFFFAOYSA-N 0.000 claims description 29
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 claims description 28
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 claims description 26
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 22
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 22
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 21
- JMMWKPVZQRWMSS-UHFFFAOYSA-N isopropanol acetate Natural products CC(C)OC(C)=O JMMWKPVZQRWMSS-UHFFFAOYSA-N 0.000 claims description 19
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 18
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 14
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 claims description 13
- GWYFCOCPABKNJV-UHFFFAOYSA-N beta-methyl-butyric acid Natural products CC(C)CC(O)=O GWYFCOCPABKNJV-UHFFFAOYSA-N 0.000 claims description 13
- FBUKVWPVBMHYJY-UHFFFAOYSA-N nonanoic acid Chemical compound CCCCCCCCC(O)=O FBUKVWPVBMHYJY-UHFFFAOYSA-N 0.000 claims description 13
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 claims description 12
- 239000000284 extract Substances 0.000 claims description 12
- OBETXYAYXDNJHR-SSDOTTSWSA-M (2r)-2-ethylhexanoate Chemical compound CCCC[C@@H](CC)C([O-])=O OBETXYAYXDNJHR-SSDOTTSWSA-M 0.000 claims description 11
- OXQGTIUCKGYOAA-UHFFFAOYSA-N 2-Ethylbutanoic acid Chemical compound CCC(CC)C(O)=O OXQGTIUCKGYOAA-UHFFFAOYSA-N 0.000 claims description 11
- FFWSICBKRCICMR-UHFFFAOYSA-N 5-methyl-2-hexanone Chemical compound CC(C)CCC(C)=O FFWSICBKRCICMR-UHFFFAOYSA-N 0.000 claims description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 9
- 150000002825 nitriles Chemical class 0.000 claims description 9
- 235000019260 propionic acid Nutrition 0.000 claims description 9
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 9
- XYHKNCXZYYTLRG-UHFFFAOYSA-N 1h-imidazole-2-carbaldehyde Chemical compound O=CC1=NC=CN1 XYHKNCXZYYTLRG-UHFFFAOYSA-N 0.000 claims description 8
- GWYFCOCPABKNJV-UHFFFAOYSA-M 3-Methylbutanoic acid Natural products CC(C)CC([O-])=O GWYFCOCPABKNJV-UHFFFAOYSA-M 0.000 claims description 8
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 8
- HCFAJYNVAYBARA-UHFFFAOYSA-N 4-heptanone Chemical compound CCCC(=O)CCC HCFAJYNVAYBARA-UHFFFAOYSA-N 0.000 claims description 8
- AWQSAIIDOMEEOD-UHFFFAOYSA-N 5,5-Dimethyl-4-(3-oxobutyl)dihydro-2(3H)-furanone Chemical compound CC(=O)CCC1CC(=O)OC1(C)C AWQSAIIDOMEEOD-UHFFFAOYSA-N 0.000 claims description 8
- GHVNFZFCNZKVNT-UHFFFAOYSA-N Decanoic acid Natural products CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 claims description 8
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims description 8
- 150000002148 esters Chemical class 0.000 claims description 8
- 235000019253 formic acid Nutrition 0.000 claims description 8
- CATSNJVOTSVZJV-UHFFFAOYSA-N heptan-2-one Chemical compound CCCCCC(C)=O CATSNJVOTSVZJV-UHFFFAOYSA-N 0.000 claims description 8
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 claims description 8
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 claims description 8
- 150000002576 ketones Chemical class 0.000 claims description 8
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 8
- XNLICIUVMPYHGG-UHFFFAOYSA-N pentan-2-one Chemical compound CCCC(C)=O XNLICIUVMPYHGG-UHFFFAOYSA-N 0.000 claims description 8
- QQZOPKMRPOGIEB-UHFFFAOYSA-N 2-Oxohexane Chemical compound CCCCC(C)=O QQZOPKMRPOGIEB-UHFFFAOYSA-N 0.000 claims description 7
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 claims description 7
- 238000004821 distillation Methods 0.000 claims description 7
- 150000002170 ethers Chemical class 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 7
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 6
- GYSCBCSGKXNZRH-UHFFFAOYSA-N 1-benzothiophene-2-carboxamide Chemical compound C1=CC=C2SC(C(=O)N)=CC2=C1 GYSCBCSGKXNZRH-UHFFFAOYSA-N 0.000 claims description 6
- HXVNBWAKAOHACI-UHFFFAOYSA-N 2,4-dimethyl-3-pentanone Chemical compound CC(C)C(=O)C(C)C HXVNBWAKAOHACI-UHFFFAOYSA-N 0.000 claims description 6
- ZPVFWPFBNIEHGJ-UHFFFAOYSA-N 2-octanone Chemical compound CCCCCCC(C)=O ZPVFWPFBNIEHGJ-UHFFFAOYSA-N 0.000 claims description 6
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 6
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 6
- 239000005642 Oleic acid Substances 0.000 claims description 6
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 6
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 claims description 6
- 235000021355 Stearic acid Nutrition 0.000 claims description 6
- DTOSIQBPPRVQHS-PDBXOOCHSA-N alpha-linolenic acid Chemical compound CC\C=C/C\C=C/C\C=C/CCCCCCCC(O)=O DTOSIQBPPRVQHS-PDBXOOCHSA-N 0.000 claims description 6
- 235000020661 alpha-linolenic acid Nutrition 0.000 claims description 6
- NMJJFJNHVMGPGM-UHFFFAOYSA-N butyl formate Chemical compound CCCCOC=O NMJJFJNHVMGPGM-UHFFFAOYSA-N 0.000 claims description 6
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 claims description 6
- 229940106681 chloroacetic acid Drugs 0.000 claims description 6
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 6
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 6
- KQQKGWQCNNTQJW-UHFFFAOYSA-N linolenic acid Natural products CC=CCCC=CCC=CCCCCCCCC(O)=O KQQKGWQCNNTQJW-UHFFFAOYSA-N 0.000 claims description 6
- 229960004488 linolenic acid Drugs 0.000 claims description 6
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 claims description 6
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 6
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 6
- 235000021313 oleic acid Nutrition 0.000 claims description 6
- 239000008117 stearic acid Substances 0.000 claims description 6
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 5
- GJRQTCIYDGXPES-UHFFFAOYSA-N iso-butyl acetate Natural products CC(C)COC(C)=O GJRQTCIYDGXPES-UHFFFAOYSA-N 0.000 claims description 5
- 229940011051 isopropyl acetate Drugs 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- HVZJRWJGKQPSFL-UHFFFAOYSA-N tert-Amyl methyl ether Chemical compound CCC(C)(C)OC HVZJRWJGKQPSFL-UHFFFAOYSA-N 0.000 claims description 4
- PZHIWRCQKBBTOW-UHFFFAOYSA-N 1-ethoxybutane Chemical compound CCCCOCC PZHIWRCQKBBTOW-UHFFFAOYSA-N 0.000 claims description 3
- OITMBHSFQBJCFN-UHFFFAOYSA-N 2,5,5-trimethylcyclohexan-1-one Chemical compound CC1CCC(C)(C)CC1=O OITMBHSFQBJCFN-UHFFFAOYSA-N 0.000 claims description 3
- AVMSWPWPYJVYKY-UHFFFAOYSA-N 2-Methylpropyl formate Chemical compound CC(C)COC=O AVMSWPWPYJVYKY-UHFFFAOYSA-N 0.000 claims description 3
- SYBYTAAJFKOIEJ-UHFFFAOYSA-N 3-Methylbutan-2-one Chemical compound CC(C)C(C)=O SYBYTAAJFKOIEJ-UHFFFAOYSA-N 0.000 claims description 3
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 claims description 3
- RMOUBSOVHSONPZ-UHFFFAOYSA-N Isopropyl formate Chemical compound CC(C)OC=O RMOUBSOVHSONPZ-UHFFFAOYSA-N 0.000 claims description 3
- IJMWOMHMDSDKGK-UHFFFAOYSA-N Isopropyl propionate Chemical compound CCC(=O)OC(C)C IJMWOMHMDSDKGK-UHFFFAOYSA-N 0.000 claims description 3
- 235000021314 Palmitic acid Nutrition 0.000 claims description 3
- KFNNIILCVOLYIR-UHFFFAOYSA-N Propyl formate Chemical compound CCCOC=O KFNNIILCVOLYIR-UHFFFAOYSA-N 0.000 claims description 3
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- 229920002678 cellulose Polymers 0.000 claims description 3
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 claims description 3
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- VNKYTQGIUYNRMY-UHFFFAOYSA-N methoxypropane Chemical compound CCCOC VNKYTQGIUYNRMY-UHFFFAOYSA-N 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 claims description 3
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- 125000005497 tetraalkylphosphonium group Chemical group 0.000 claims description 3
- PYVOHVLEZJMINC-UHFFFAOYSA-N trihexyl(tetradecyl)phosphanium Chemical class CCCCCCCCCCCCCC[P+](CCCCCC)(CCCCCC)CCCCCC PYVOHVLEZJMINC-UHFFFAOYSA-N 0.000 claims description 3
- MNWFXJYAOYHMED-UHFFFAOYSA-N heptanoic acid group Chemical group C(CCCCCC)(=O)O MNWFXJYAOYHMED-UHFFFAOYSA-N 0.000 claims description 2
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- 238000012546 transfer Methods 0.000 description 1
- KAKQVSNHTBLJCH-UHFFFAOYSA-N trifluoromethanesulfonimidic acid Chemical compound NS(=O)(=O)C(F)(F)F KAKQVSNHTBLJCH-UHFFFAOYSA-N 0.000 description 1
- ZYZKJPDNPIOQKC-UHFFFAOYSA-M trihexyl(tetradecyl)phosphanium;acetate Chemical compound CC([O-])=O.CCCCCCCCCCCCCC[P+](CCCCCC)(CCCCCC)CCCCCC ZYZKJPDNPIOQKC-UHFFFAOYSA-M 0.000 description 1
- ZVGFSDSNXDNLBC-UHFFFAOYSA-M trihexyl(tetradecyl)phosphanium;formate Chemical compound [O-]C=O.CCCCCCCCCCCCCC[P+](CCCCCC)(CCCCCC)CCCCCC ZVGFSDSNXDNLBC-UHFFFAOYSA-M 0.000 description 1
- RNONQEYAHNKSFG-UHFFFAOYSA-M trihexyl(tetradecyl)phosphanium;hydroxide Chemical compound [OH-].CCCCCCCCCCCCCC[P+](CCCCCC)(CCCCCC)CCCCCC RNONQEYAHNKSFG-UHFFFAOYSA-M 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-M valerate Chemical compound CCCCC([O-])=O NQPDZGIKBAWPEJ-UHFFFAOYSA-M 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
- 235000021419 vinegar Nutrition 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D11/00—Solvent extraction
- B01D11/04—Solvent extraction of solutions which are liquid
- B01D11/0492—Applications, solvents used
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
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- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
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- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/43—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation
- C07C51/44—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation by distillation
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- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/30—Phosphinic acids [R2P(=O)(OH)]; Thiophosphinic acids ; [R2P(=X1)(X2H) (X1, X2 are each independently O, S or Se)]
- C07F9/301—Acyclic saturated acids which can have further substituents on alkyl
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Abstract
The invention relates to a method for extracting C from an aqueous stream1To C4A solvent for the carboxylic acid. More specifically, the extraction solvent comprises one or more salts comprised of tetraalkylphosphonium cations and carboxylate anions. The extraction solvent may further comprise one or more non-ionic liquid organic solvents as an enhancer. The extraction solvent can be used to extract an aqueous mixture containing one or more lower carboxylic acids, such as monocarboxylic acids, alkoxycarboxylic acids, and halogen-containing carboxylic acids.
Description
Cross reference to related applications
The present application claims the benefit of provisional application No. 62/094,238 filed 2014 12, 19, § 119(e) (1); the entire contents of this provisional application are incorporated herein by reference.
Technical Field
The present invention generally relates to methods for extracting C from aqueous streams1To C4Solvents for carboxylic acids, compositions containing them and methods for separating acids from water.
Background
Recovery of C from aqueous streams1To C4Carboxylic acids (hereinafter "lower acids") are common industrial problems arising from various reactions and processing steps. Simple distillation of wet acid stream to recover glacial acid suffers from unfavorable vapor-liquid equilibrium (VLE) and all C1To C4The high energy cost of carboxylic acids hinders. Examples of adverse VLEs include formic acid-water highest boiling point homogeneous azeotropes, acetic acid-water VLE "pinches" (regions of low relative volatility), and water and all C3-C4The lowest boiling point homogeneous azeotrope of carboxylic acid.
Various methods have been proposed in the art to address the problem of recovering lower acids from wet acid feeds. For example, one method subjects an aqueous solution of a lower acid to azeotropic distillation with an entraining component that forms a heterogeneous minimum boiling azeotrope with water such that the azeotrope boils at a temperature significantly lower than pure water, pure lower acid, and any acid-water azeotrope. The extraction step is usually preceded by azeotropic distillation. The extraction step partitions the carboxylic acid into a water immiscible solvent (which is typically the same as the azeotropic entrainer) to remove most of the water from the recovered acid. Have been in the artNumerous examples of azeotropic distillation, extraction, and combinations thereof using conventional organic solvents are presented. These include U.S. patent nos. 1,839,894; 1,860,512, respectively; 1,861,841, respectively; 1,917,391, respectively; 2,028,800, respectively; 2,050,234, respectively; 2,063,940, respectively; 2,076,184, respectively; 2,123,348, respectively; 2,157,143, respectively; 2,184,563, respectively; 2,199,983, respectively; 2,204,616, respectively; 2,269,163, respectively; 2,275,834, respectively; 2,275,862, respectively; 2,275,867, respectively; 2,317,758, respectively; 2,333,756, respectively; 2,359,154, respectively; 2,384,374, respectively; 2,395,010, respectively; 2,537,658, respectively; 2,567,244, respectively; 2,854,385, respectively; 3,052,610, respectively; and 5,662,780 and Eaglesifield et al, "Recovery of Acetic Acid from soluble Aqueous Solutions by Liquid-Liquid Extraction-Part 1,") "The Industrial ChemistVol 29, page 147-.
Several solvent characteristics determine the capital and energy costs of the extractive-distillation process for the extractive recovery of lower acids from wet acid feeds. The solvent used in this extraction process is immiscible with water and meets two criteria:
a) the solvent exhibits some selectivity between the extraction of carboxylic acid and water, i.e., the carboxylic acid/water ratio in the extraction solvent after extraction is significantly greater than in the wet acid feed stream. This factor can be quantified as the water/acid weight ratio in the extract stream as defined in more detail below;
b) the solvent exhibits sufficient affinity and capacity for lower carboxylic acids,
these characteristics can be quantified by an equilibrium partition coefficient determined experimentally as defined in more detail below.
The equilibrium partition coefficient (which may also be used interchangeably with the term "partition coefficient") of component a (lower carboxylic acid) is defined as follows:
the partition coefficient is a measure of the relative concentration of the solute to be extracted in the two phases. The value of the acid partition coefficient is directly related to the amount of solvent needed to achieve a given extraction. A low value of the partition coefficient indicates that a high amount of solvent is required and a high value of the partition coefficient indicates that a low amount of solvent is required. Since the acid partition coefficient varies with acid concentration, the minimum amount of solvent required to achieve a given amount of acid extraction also varies. Thus, the control solvent flow requirement for extraction depends on the lowest value of the acid partition coefficient, as the acid concentration changes from a high value of the inlet wet acid feed to a low value of the outlet acid concentration of the effluent raffinate stream.
The control acid distribution coefficient can be defined as:
Pcont= minimum value (P)raff, Pextr)
Wherein
Praff= acid partition coefficient at near the desired acid concentration in the raffinate stream (i.e. at low acid concentration); and
Pextr= acid partition coefficient at an acid concentration close to that required in the extract stream, i.e. at high acid concentration.
The most important water-acid selectivity values are those at the extraction end of the extraction cascade. It is defined as:
Rextr = Wextr / Aextr
wherein
Wextr= weight fraction of water in the extraction product stream; and is
Aextr= weight fraction of acid in the extraction product stream.
Controlling the distribution coefficient PcontAnd the extraction water/acid ratio RextrCan be combined to yield a total extraction factor epsilon, which is a simple measure of the effectiveness of a given solvent in recovering lower acids from a wet acid feed in an extractive-distillation process. The extraction factor epsilon is defined as:
ε = Pcont /Rextr = (Pcont* Aextr) / Wextr
generally, the higher the extraction factor, the lower the capital and energy costs for a given extraction.
Extraction solvents that exhibit reverse behavior are also known. That is, their acid partition coefficients are lowest at the extraction end (high acid concentration) and highest at the raffinate end (low acid concentration) of the cascade. Examples of such solvents include nitriles, phosphate esters, phosphine oxides (U.S. patent nos. 3,816,524 and 4,909,939), and amines (for example)Such as King, "Amine-Based Systems for Carboxylic Acid Recovery: scientific Amines and the property Choice of solvent Extraction and Recovery from Water," CHEMTECH, Vol.5, p.285-291 (1992); and Tamada et al, "Extraction of Carboxylic Acids with Amine extracts. 2. Chemical Interactions and Interpretation of Data"Ind. Eng. Chem. Res.Volume 29, page 1327-1333 (1990)).
This reverse behavior is also observed for the following (partition coefficient is highest at low acid concentrations): phosphonium-and ammonium-phosphinate ionic liquids (Blauser et al, "Extraction of butyl acid with a solvent containing ammonium ionic liquid"Sep. Purif. Technol.,Volume 119, page 102-111 (2013); martak et al, "phosphorus ionic liquids as new, reactive extrectants of lactic acid"Chem. PapersVol.60, pp.395-98 (2006)) and Phosphonium carboxylates (Oliveira et al, "Extraction of L-Lactic, L-Malic, and Succinic Acids Using phosphorus-Based Ionic Liquids"Sep. Purif. Tech.,Volume 85, page 137 and 146 (2012)). In particular, Oliveira et al reported that P was present in most lactic, succinic and malic acid extraction tests666,14Decanoate does not form a simple two-phase system. The third phase complicates the distribution and recovery of the carboxylic acid.
Poole et al, "Extraction of Organic Compounds with Room Temperature Ionic Liquids"J. Chromatogr. (A)The use of hydrophobic ionic liquids as extraction solvents has been reviewed at 1217, 2268, 2286 (2010). Robertson et al, "Industrial Preparation of phosphorus Ionic Liquids",Green Chem.the development and advantages of Phosphonium Ionic Liquids have been reviewed in volume 5, page 143-152 (2003) and their use for extracting Ethanol from fermentation broths by Neves et al, "Separation of Ethanol-Water Mixtures by Liquid-Liquid Extraction Using Phosphonium-Based Ionic Liquids"Green Chem.Volume 13, pages 1517-1526 (2011) are addressed.
The extraction of lower carboxylic acids using imidazolium and phosphonium ionic liquids has also been reported.For acetic acid, McFarlane et al report bmim-NTf2、omim-NTf2、bmim-PF6、P666,14-LABS/nonanol, P444,14-LABS/nonanol and P666,14-OSO2Me(“Room Temperature Ionic Liquids for Separating Organics from Produced Waters,” Sep. Sci. & Tech.Vol 40, 1245-. Hashikawa claims P for acetic, propionic, and butyric acids222,8-NTf2("Method for Producing Acetic Acid," JP 2014/40389, Daicel, (3/6/2014)). And Matsumoto et al reported bmim-PF6、hmim-PF6And omim-PF6(“Extraction of Organic Acids Using Imidazolium-Based Ionic Liquids and Their Toxicity to Lactobacillus rhamnosus,” Sep. and Purif. Tech.Volume 40, pages 97-101 (2004)).
However, none of these documents uses quaternary phosphonium carboxylates with monofunctional carboxylic acids. Furthermore, the lower carboxylic acid partition was poor in the reports of McFarlane, Hashikawa and Matsumoto. Furthermore, those skilled in the art recognize that the addition of an alcohol to a phosphonium ionic liquid composition for the extraction of lower carboxylic acids is not preferred due to the formation of carboxylic ester derivatives of the alcohol with acid extracts, particularly in downstream distillation or evaporation processes for the purification of lower carboxylic acids. This exclusion is achieved by Judson King, "Acetic Acid Extraction"Handbook of Solvent ExtractionKrieger publication. Co. (1991) was solved.
In particular, Hashikawa only claims the use of ionic liquids with fluorine-containing anions, such as bis (fluorosulfonyl) imide, bis (fluoroalkylsulfonyl) imide, tris (perfluoroalkyl) trifluorophosphate, hexafluorophosphate, tetrafluoroborate and perfluoroalkylsulfonate. These anions add significant cost and toxicity problems for large scale applications. Furthermore, Hashikawa claims ionic liquids having phosphonium salts containing a total of only 10 carbon atoms or more. According to the data presented in the Hashikawa application, triethyl (octyl) phosphonium bis (trifluoromethylsulfonyl) amide shows relatively poor extraction behavior towards acetic acid, with small two-phase region, low acetic acid capacity and very low partition coefficient (between about 0.06 to 0.1).
Despite the poor performance of the ionic liquid systems reported and claimed above, the very low vapor pressure of ionic liquids remains an attractive physical property for the lower carboxylic acid extract phase. Thus, there is a need in the art for an extraction solvent that provides excellent partitioning of lower carboxylic acids from aqueous solutions and enables simple separation of these acids from the solvent via distillation. There is also a need for an extraction solvent with a high extraction factor whereby C can be recovered from wet acid feed in an energy and cost effective manner1To C4A carboxylic acid.
These needs and others are addressed by the present invention, which is apparent from the following description and appended claims.
Summary of The Invention
The invention is set forth in the following detailed description and the appended claims.
Briefly, in one aspect, the present invention provides a method for extracting C from water1To C4A solvent for the carboxylic acid. The extraction solvent comprises (a) a quaternary phosphonium carboxylate salt and (b) a non-ionic organic solvent, with the proviso that the non-ionic organic solvent is not an extract. The carboxylate has the general formula 1:
wherein
R1、R2、R3And R4Each independently is C1To C26A hydrocarbon group, provided that R1、R2、R3And R4A total of at least 24 carbon atoms; and is
R5Is hydrogen or C1To C24A non-aromatic hydrocarbon group.
In another aspect, the present invention provides a method for mixing C1To C4Composition of carboxylic acid separated from water. The composition comprises:
(a) quaternary phosphonium carboxylates according to the invention;
(b) a non-ionic organic solvent according to the invention;
(c) C1to C4A carboxylic acid; and
(d) and (3) water.
In yet another aspect, the present invention provides a method of treating a mammal with C1To C4A process for separating carboxylic acid from water. The method comprises the step of enabling the catalyst to contain C1To C4A feed mixture of carboxylic acid and water is contacted with an extraction solvent according to the present invention in an effective manner to form (a) a mixture comprising the carboxylic acid salt, the non-ionic organic solvent, and at least a portion of C from the feed mixture1To C4An extraction mixture of carboxylic acids and (b) a feed mixture comprising water and less C than the feed mixture1To C4A raffinate mixture of carboxylic acids.
In one aspect, the invention relates to a process for separating acetic acid from water. The process comprises contacting a feed mixture comprising acetic acid and water with an extraction solvent comprising a quaternary phosphonium carboxylate salt according to the present invention under conditions effective to form (a) an extraction mixture comprising the carboxylate salt and at least a portion of the acetic acid from the feed mixture and (b) a raffinate mixture comprising water and less acetic acid than the feed mixture.
Brief description of the drawings
The figure shows P at 300 MHz from example 2666,14-2EH in CDCl3In (1)1H NMR spectrum.
Detailed Description
It has been surprisingly found that when certain quaternary phosphonium carboxylates are combined with an aqueous solution of a lower carboxylic acid, the resulting partitioning of the lower acid into the phosphonium carboxylate phase can be quite high, particularly when the concentration of the lower acid is low (e.g., < 5% by weight). The carboxylic acid salts exhibit excellent low acid extraction selectivity over co-extraction with water. Thus, the carboxylate salts have an extraction factor epsilon significantly higher than other types of lower acid extraction solvents and are therefore particularly useful for the recovery of lower acids from wet-process acid streams.
Accordingly, in one aspect, the present invention provides quaternary phosphonium carboxylates useful for separating lower acids from aqueous streams. The carboxylate is depicted by formula 1:
wherein
R1、R2、R3And R4Each independently is C1To C26A hydrocarbon group, provided that R1、R2、R3And R4A total of at least 24 carbon atoms; and is
R5Is hydrogen or C1To C24A non-aromatic hydrocarbon group.
The term "hydrocarbyl" as used herein refers to a group containing hydrogen and carbon atoms and may be straight or branched chain, cyclic or acyclic, and saturated or unsaturated.
R1、R2、R3And R4Each may have the same number of carbon atoms or may have different lengths. In one embodiment, R1、R2、R3And R4Having a total of not more than 54 carbon atoms. In another embodiment, R1、R2、R3And R4Each having at least 6 carbon atoms. In other embodiments, R1、R2、R3And R4Each containing 6 to 24 carbon atoms, 6 to 20 carbon atoms, 6 to 18 carbon atoms, 6 to 14 carbon atoms, or 8 to 14 carbon atoms.
Preferably, R5Having a length such that the length of the (C) is equal to that of the (C) phosphonium group [ PR ] as defined above1R2R3R4]In combination, the carboxylate anion renders the salt hydrophobic. In one embodiment, R5Is C3To C9A non-aromatic hydrocarbon group. In another embodiment, R5Is C3To C20A non-aromatic hydrocarbon group. In other embodiments, R5May contain 1 to 20 carbon atoms, 1 to18 carbon atoms, 1 to 16 carbon atoms, 1 to 14 carbon atoms, 1 to 12 carbon atoms, 3 to 20 carbon atoms, 3 to 18 carbon atoms, 3 to 16 carbon atoms, 3 to 14 carbon atoms, or 3 to 12 carbon atoms. R5May contain functional groups such as alkoxy, olefinic and halogen functional groups.
By "hydrophobic" is meant that the salt is immiscible in water under typical extraction conditions, e.g., has less than 5 wt% miscibility in water at 20 ℃.
The carboxylate is liquid under typical extraction conditions.
Examples of phosphonium carboxylates having the structure of formula 1 are listed in table 1 below. If the compounds are known, their CAS registry numbers are also listed.
TABLE 1
CAS registry number for some known phosphonium carboxylates
a Pure & Appl. Chem.Vol 84, page 723 (2012)
b Green Chem.Vol.7, page 855 (2005)
c U.S. Pat. No. 5,663,422 (Eastman Chemical; 1997)
NF = not found.
Carboxylate derivatives in table 1 that do not have CAS accession numbers are not previously known and are therefore specifically considered to be within the scope of the present invention.
Mixtures containing more than one quaternary cation and more than one carboxylate anion may also be used to extract lower acids from aqueous solutions and are therefore also considered to be within the scope of the present invention.
In one embodiment, the carboxylate salt comprises a tetraalkylphosphonium salt of formic acid, acetic acid, propionic acid, n-butyric acid, isobutyric acid, n-valeric acid, isovaleric acid, n-hexanoic acid, 2-ethylbutyric acid, heptanoic acid, n-octanoic acid, 2-ethylhexanoic acid, nonanoic acid, decanoic acid, dodecanoic acid, palmitic acid, stearic acid, oleic acid, linolenic acid, mixed plant-derived acids, or chloroacetic acid.
In another embodiment, the carboxylate salt comprises a trihexyl (tetradecyl) phosphonium salt of formic, acetic, propionic, n-butyric, isobutyric, n-valeric, isovaleric, n-hexanoic, 2-ethylbutyric, heptanoic, n-octanoic, 2-ethylhexanoic, nonanoic, decanoic, dodecanoic, palmitic, stearic, oleic, linolenic, mixed plant-derived acids, or chloroacetic acid.
In yet another embodiment, the carboxylate salt comprises trihexyl (tetradecyl) phosphonium carboxylate. The carboxylic anion may be selected from formate, acetate, propionate, acrylate, butyrate, isobutyrate, methacrylate, hexanoate, 2-ethylbutyrate, octanoate, 2-ethylhexanoate, nonanoate, and decanoate.
Some phosphonium carboxylates having the structure of formula 1 are commercially available, while others can be made by known methods from readily available precursors. See, e.g., Kogelnig et al, "Green Synthesis of New Ammonium Ionic Liquids and the third polar as Extracting Agents"Tetrahedron LettersVol.49, pp.2782-2785 (2008) and Ferguson et al, "A Greener, Halide-Free Approach to Ionic Liquid Synthesis"Pure & Appl. Chem.Vol 84, page 723 and 744 (2012). The former process involves the metathesis of alkali metal carboxylates with quaternary ammonium halides, the latter process uses ion exchange resins, and in our experience (see examples 1 and 2 below) produces ionic liquids with lower amounts of residual halide. One example of a readily available precursor is trihexyl (tetradecyl) phosphonium chloride.
Thus, while synthetic methods of general nature for the preparation of quaternary phosphonium carboxylates are known, relatively small quantities are prepared and their use for the extraction of lower acids from aqueous streams is unknown, except for P for the extraction of lactic, malic and succinic acids reported by Oliveira et al and described herein666,14-decanoic acid salt. Thus, in one embodiment, the present invention excludes the use of P alone666,14-decanoic acidSalts for the extraction of aqueous solutions of lactic, malic and succinic acids.
In a second aspect, the present invention provides composition a:
composition a represents a unique biphasic mixture comprising a quaternary phosphonium carboxylate according to formula 1, a lower acid and water. Other materials may also be present. Composition a can be used to separate lower acids from water.
As mentioned above, the lower acid means C1To C4A carboxylic acid. For example, the carboxylic acid may be a monocarboxylic acid or, an alkoxy carboxylic acid or a halogen containing carboxylic acid. Examples of such acids include formic acid, acetic acid, propionic acid, acrylic acid, n-butyric acid, isobutyric acid, methacrylic acid, chloroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, methoxyacetic acid, and the like. In one embodiment, the C1To C4The carboxylic acid is a monocarboxylic acid containing no hydroxyl group.
Producing a diluted aqueous carboxylic acid-containing stream (i.e., comprising less than 1 wt.% to 60 wt.% C in the aqueous mixture)1To C4Examples of processes for the production of cellulose esters or terephthalic acid, the production of ketene or higher enones from the high temperature dehydration of carboxylic acids and anhydrides, the hydrolysis of poly (vinyl acetate), the production of fischer-tropsch liquids, the production of oil and gas (producing "produced water"), the ketonization of carboxylic acids to ketones, the oxidation of ethylene to acetaldehyde by the Wacker process, the oxidation of propylene to acrylic acid, the oxidation of oxo-aldehydes to their carboxylic acids, the hydrocarboxylation of formaldehyde with water and carbon monoxide, the oxidation of isobutylene to methacrylic acid, pyroligneous acid, fermentation broths, acetic acid streams (vinegar stream), and the like. By acetic acid stream is meant an aqueous stream comprising acetic acid. In one embodiment, the wet acid feed is derived from the production of cellulose esters.
The wet acid feed may comprise 0.5 to 60 wt% of one or more C1To C4A carboxylic acid. More preferably, the wet acid feed comprises 0.5 to 35 wt% C1To C4Carboxylic acids. Due to the exceptionally high acid partition coefficient of the inventive carboxylic acid salts even at low acid concentrations, the inventive extraction solvents can be advantageously used for extracting lower acids at concentrations as low as 0.5 wt.% in wet acid feeds.
The terms "feed" and "feed mixture" as used herein are intended to have their commonly understood meaning in the field of liquid-liquid extraction, which is a solution containing the material to be extracted or separated. In the present invention, an example of the "feed" is a mixture composed of one or more of formic acid, acetic acid, propionic acid, acrylic acid, n-butyric acid, isobutyric acid, methacrylic acid, methoxyacetic acid, chloroacetic acid, dichloroacetic acid, trichloroacetic acid and trifluoroacetic acid in water. In the present invention, the terms "feed" and "feed mixture" are synonymous with "aqueous acid stream", "weak acid stream" and "wet acid feed".
The term "extraction solvent" as used herein is intended to be synonymous with the term "extractant" and means a water-immiscible or hydrophobic liquid used in extraction processes to extract materials or solutes from a feed.
The weight ratio of carboxylate to wet acid feed in composition a can vary over a wide range. For example, the ratio may be 0.2 to 10:1, or more preferably 0.3 to 4: 1.
One feature of composition a is that it separates into two phases, an aqueous phase and an organic phase, with the lower acid partitioning between them. The biphasic nature of composition a is desirable to physically separate the lower acid from the aqueous solution. The amount of lower acid partitioned between the phases is limited only by the two-phase nature of the system. The amount of lower acid preferably does not exceed a level at which the biphasic nature of the composition is lost. Other materials may also be present, but only to the extent that the biphasic nature of the system is retained. Complex systems that form more than two phases are not preferred because such systems obscure the effective separation of lower acids (obscure).
Formation of more than two-phase systems, emulsions, or other complex mixtures of quaternary phosphonium carboxylates can be simplified by adding a hydrophobic, non-ionic organic co-solvent to the quaternary phosphonium carboxylate extraction phase.
Therefore, in the third aspect,the present invention provides a process for extracting lower carboxylic acid (C) from water1 - C4) The solvent of (1). The extraction solvent comprises a phosphonium carboxylate defined by the above formula 1 and a non-ionic organic (NIO) solvent. The NIO solvent is not an extract (i.e., C to be separated)1 - C4Carboxylic acid). Rather, it is separated from and distinct from the lower carboxylic acid to be separated.
The extraction solvent can comprise two or more carboxylic acid salts.
The NIO solvent is preferably selected to impart desirable physical properties to the extraction solvent, such as lower viscosity or higher hydrophobicity, or to provide a composition as described above and described in, for example, U.S. Pat. Nos. 1,861,841; 1,917,391, respectively; 2,028,800, respectively; 3,052,610, respectively; 5,662,780, respectively; 2,076,184, respectively; and 2,204,616 with water to enable drying of the lower carboxylic acid in subsequent purification steps.
Examples of such hydrophobic NIO solvents include ketones, aromatic hydrocarbons, saturated hydrocarbons, ethers, esters, chlorinated hydrocarbons, nitriles, and higher carboxylic acids.
Fatty alcohols, such as nonanol, are not preferred because these may complicate the isolation of the lower acids by forming esters during extraction or subsequent purification. In one embodiment, the NIO solvent excludes fatty alcohols, such as nonanol.
Also care should be taken in selecting a particular compound from any of the above classes of co-solvents that, in combination with a lower acid or water, may form an azeotrope or may be difficult to separate from the lower acid.
Preferred non-ionic organic solvents form a minimum boiling azeotrope with water, but do not form an azeotrope with the lower acid.
In one embodiment, the NIO solvent has 4 to 20 carbon atoms. In another embodiment, the NIO solvent has 4 to 18 carbon atoms. In other embodiments, the NIO solvent has 4 to 16 carbon atoms, 4 to 14 carbon atoms, 4 to 12 carbon atoms, 5 to 20 carbon atoms, 5 to 18 carbon atoms, 5 to 16 carbon atoms, 5 to 14 carbon atoms, or 5 to 12 carbon atoms.
In a particular embodiment, the NIO solvent comprises a higher carboxylic acid. Notably, it has been found that as little as 10 mole percent of higher carboxylic acid in the extraction solvent can significantly increase the partition coefficient of lower acid, particularly at low concentrations in the wet acid stream.
As used herein, "higher carboxylic acid" refers to carboxylic acids having 4 to 20 carbon atoms. In the case where the carboxylic acid to be separated has 4 carbon atoms, the "higher carboxylic acid" contains at least 5 carbon atoms or has a boiling point sufficiently different (e.g. +/-2 ℃) than the lower acid to be separated so that the two can be separated from each other by simple distillation.
In one embodiment, the higher carboxylic acid is selected from the group consisting of n-butyric acid, isobutyric acid, n-valeric acid, isovaleric acid, n-hexanoic acid, 2-ethylbutyric acid, heptanoic acid, n-octanoic acid, 2-ethylhexanoic acid, nonanoic acid, decanoic acid, dodecanoic acid, stearic acid, oleic acid, linolenic acid, and mixed plant-derived acids.
In another embodiment, the higher carboxylic acid is selected from the group consisting of n-butyric acid, isobutyric acid, n-valeric acid, isovaleric acid, n-hexanoic acid, 2-ethylbutyric acid, heptanoic acid, n-octanoic acid, and 2-ethylhexanoic acid.
Preferred NIO esters are those containing 4 to 6 carbon atoms, such as ethyl acetate, n-propyl formate, isopropyl acetate, isopropyl formate, n-butyl acetate, n-butyl formate, isobutyl acetate, isobutyl formate, n-propyl propionate, and isopropyl propionate.
Preferred NIO ketones are those containing from 5 to 9 carbon atoms, such as 2-pentanone, 3-methyl-2-butanone, 2-hexanone, 2-heptanone, cyclohexanone, 4-methyl-2-pentanone, 2, 4-dimethyl-3-pentanone, 5-methyl-2-hexanone, 4-heptanone, 2-octanone, 5-nonanone, 2, 8-dimethyl-4-heptanone, 3, 5-trimethylcyclohexanone, and isophorone.
Preferred NIO ethers are those containing 4 to 8 carbon atoms, such as diethyl ether, methyl propyl ether, dipropyl ether, di-isopropyl ether, methyl tert-butyl ether, tert-amyl methyl ether, and ethyl butyl ether.
Preferred NIO aromatics include toluene, meta-xylene, para-xylene, and ortho-xylene.
Preferred NIO chlorinated hydrocarbons include dichloromethane, chloroform, dichloroethane, ethylene chloride, carbon tetrachloride and chlorinated derivatives of benzene.
Preferred NIO nitriles include valeronitrile and nitriles boiling above valeronitrile such as capronitrile and benzonitrile.
In one embodiment, the hydrophobic NIO solvent is selected from the group consisting of methyl isobutyl ketone, toluene, isopropyl acetate, and methyl tert-butyl ether.
In another embodiment, the hydrophobic NIO solvent is a fatty carboxylic acid, such as butyric, valeric, caproic, enanthic, caprylic, pelargonic, and C4-C9Isomeric forms of carboxylic acids.
The extraction solvent and compositions containing the same according to the present invention may comprise two or more NIO solvents. The use of mixtures of hydrophobic solvents optimally achieves the desired physical properties of the claimed system.
The extraction solvent of the present invention may comprise 0 to 90, 10 to 90, 20 to 90, 30 to 90, 40 to 90, or 50 to 90 weight percent of the NIO solvent. The extraction solvent may also contain 0 to 60, 10 to 60, 20 to 60, 30 to 60, 40 to 60, or 50 to 60 weight percent of a NIO solvent. The balance of the extraction solvent may be constituted by the carboxylate according to the invention.
The NIO solvent may be combined with the carboxylate salt prior to introduction into the extraction vessel. Alternatively, the NIO solvent may be introduced separately into the extraction vessel. In one embodiment, the NIO solvent may be introduced as a second solvent feed on the other side of the extraction cascade than the wet acid feed, such as in a staged extraction mode, where the NIO solvent aids in washing out any carboxylic acid salts from the final raffinate product stream.
The carboxylate salt or mixture of carboxylate salts of the present invention may be combined with one or more NIO solvents in any known manner to form an extraction solvent.
In a fourth aspect, the present invention provides composition B:
composition B comprises a carboxylate of formula 1, an NIO solvent, C1To C4Carboxylic acid and water. It can be used for mixing lower carboxylic acid with waterIsolating and optionally purifying the lower acid.
Composition B may contain more than one carboxylate, more than one NIO solvent, and/or more than one lower acid. The carboxylate salt, the NIO solvent, and the lower acid can be any of those described herein.
In one embodiment, composition B has only two liquid phases.
Composition B is characterized in that C can be recovered by distillation at atmospheric pressure or lower1To C4A carboxylic acid.
The weight ratio of extraction solvent (carboxylate and NIO solvent) to wet acid feed in composition B can vary over a wide range. For example, the ratio may be 0.2 to 10:1, or more preferably 0.3 to 4: 1.
In a fifth aspect, the present invention provides a method of treating a mammal with C1To C4A process for separating carboxylic acid from water. The method comprises the step of enabling the catalyst to contain C1To C4A feed mixture of a carboxylic acid and water is contacted with an extraction solvent comprising a quaternary phosphonium carboxylate salt according to the present invention and a nonionic organic solvent according to the present invention in an amount effective to form (a) a composition comprising the carboxylate salt, the nonionic organic solvent, and at least a portion of C from the feed mixture1To C4An extraction mixture of carboxylic acids and (b) a feed mixture comprising water and less C than the feed mixture1To C4A step of contacting under conditions of a raffinate mixture of carboxylic acids.
The extraction of the feed mixture (i.e., the contacting step) may be carried out by any means known in the art for intimately contacting two immiscible liquid phases and separating the resulting phases after the extraction procedure. For example, the extraction can be performed using columns, centrifuges, mixer-settlers, and a wide variety of devices. Some representative examples of extractors include unstirred columns (e.g., sprays, baffled trays and packings, perforated plates), agitated columns (e.g., pulsed, rotating agitated and reciprocating plates), mixer-settlers (e.g., pump-settlers, static mixer-settlers, and agitated mixer-settlers), centrifugal extractors (e.g., those produced by Robatel, Luwesta, deLaval, Dorr Oliver, Bird, CINC, and Podbielniak), and other miscellaneous extractors (e.g., emulsion phase contactors, electrically enhanced extractors, and membrane extractors). A description of these devices can be found in "Handbook of Solvent Extraction," Krieger Publishing Company, Malabar, FL, pp.275-501 (1991). The various types of extractors can be used alone or in any combination.
The extraction may be carried out in one or more stages. The number of extraction stages can be selected based on many factors, such as capital cost, achieving high extraction efficiency, ease of operation, stability of feed and extraction solvent, and extraction conditions. The extraction can also be carried out in batch or continuous mode of operation. In continuous mode, the extraction can be performed in co-current, counter-current, or as a staged extraction (where multiple solvents and/or multiple solvent feed points are used to help facilitate separation). The extraction process can also be carried out in a plurality of separation zones which can be connected in series or in parallel.
The extraction may be carried out at an extraction solvent to feed mixture weight ratio of, for example, 0.2 to 10:1, or more preferably 0.3 to 4: 1.
The extraction can generally be carried out at a temperature of from 10 to 140 ℃. For example, the extraction may be carried out at a temperature of 30 to 110 ℃. The desired temperature range may be further limited by the boiling point of the extractant component or water. Typically, it is undesirable to run the extraction under conditions where the extractant boils. In one embodiment, the extractor can be operated to establish a temperature gradient across the extractor to improve mass transfer kinetics or decantation rate.
If the temperature selected for the extraction is greater than the normal boiling point of any lower acid to be extracted, any component making up the extraction solvent, or water; the extractor can be operated at a pressure sufficient to suppress boiling of any of the above components. The extraction may generally be carried out at a pressure of from 1 bar to 10 bar, or from 1 bar to 5 bar.
The separation process of the present invention may further comprise separating the extract from the raffinate and recovering C from the extract by distillation at atmospheric pressure or lower1To C4And (3) carboxylic acid. Any known method of separating the liquid extract from the raffinate may be used. Likewise, any known distillation technique may be used to recover the solvent from the extractionA lower acid.
In one embodiment, the present invention provides a process for separating acetic acid from water. The process comprises contacting a feed mixture comprising acetic acid and water with an extraction solvent comprising a quaternary phosphonium carboxylate salt according to the present invention under conditions effective to form (a) an extraction mixture comprising the carboxylate salt and at least a portion of the acetic acid from the feed mixture and (b) a raffinate mixture comprising water and less acetic acid than the feed mixture.
This acetic acid separation process can be carried out using any of the modes described above.
The extraction solvent used in this process may further comprise one or more NIO solvents according to the invention.
The acetic acid separation process may further comprise the steps of separating the extraction mixture from the raffinate mixture and recovering acetic acid from the extraction mixture by distillation at atmospheric pressure or lower.
These additional steps may also be performed as described above.
The present invention includes and expressly contemplates any and all combinations of embodiments, features and/or ranges disclosed herein. That is, the invention may be defined by any combination of the embodiments, features and/or ranges set forth herein.
The indefinite articles "a" and "an" as used herein mean one or more than one unless the context clearly dictates otherwise. Similarly, the singular forms of nouns include their plural forms and vice versa unless the context clearly dictates otherwise.
As used herein, the term "and/or," when used in reference to a listing of two or more items, means that any one of the listed items can be used by itself or any combination of two or more of the listed items can be used. For example, if a composition is described as containing components A, B and/or C, the composition may contain only a; only contains B; only contains C; contains A and B; contains A and C; contains B and C; or A, B and C.
Notwithstanding any attempt to achieve precision, the numerical values and ranges set forth herein should be considered as approximations (even if not limited by the term "about"). These values and ranges may vary from their stated values depending on the desired properties sought to be obtained by the present invention, as well as the variations resulting from the standard deviations found in the measurement techniques. Moreover, the ranges described herein are intended and are expressly contemplated to include all sub-ranges and values within the specified range. For example, a range of 50 to 100 is intended to describe and include all values within the range, including sub-ranges such as 60 to 90 and 70 to 80.
The contents of all documents, including patent and non-patent documents, cited herein are hereby incorporated by reference in their entirety. In the event that any incorporated subject matter contradicts any disclosure herein, the disclosure herein should take precedence over the incorporated content.
The invention may be further illustrated by the following examples of preferred embodiments thereof, although it will be understood that these examples are included merely for purposes of illustration and are not intended to limit the scope of the invention.
Examples
Abbreviations used in the following examples are summarized in table 2.
TABLE 2
Abbreviations
Compound (I) | Abbreviations |
Acetic acid | HOAc |
Propionic acid | HOPr |
N-butyric acid | n-HOBu |
Isobutyric acid | i-HOBu |
2, 2-dimethylbutyric acid | 2,2-DMB acid |
2-Ethylbutyric acid | 2EB acid |
2-ethyl hexanoic acid | 2EH acid |
Nitrile butadiene | PrCN |
Methyl tert-butyl ether | MTBE |
Tert-amyl methyl ether | TAME |
4-heptanone | DPK |
Ethyl acetate | EtOAc |
Acetic acid isopropyl ester | i-PrOAc |
N-propyl acetate | n-PrOAc |
Acetic acid n-butyl ester | n-BuOAc |
Acetic acid isobutyl ester | i-BuOAc |
2-pentanone | MPK |
4-methyl-2-pentanone | MIBK |
5-methyl-2-hexanones | MIAK |
2-heptanone | MAK |
Phosphoric acid tributyl ester | TBP |
Triethyl phosphate | TEHP |
Cyanex 923 mixture of trialkyl phosphine oxides with octyl and hexyl groups | C923 |
1-ethyl-3-methylimidazolium bis (trifluoromethylsulfonyl) amide | emim-NTf2 |
1-butyl-3-methylimidazolium bis (trifluoromethylsulfonyl) amide | bmim-NTf2 |
1-butyl-3-methylimidazolium acetate | bmim-OAc |
1-butyl-3-methylimidazolium bis (trifluoro)Ethylsulfonyl) amide | bmim-BETI |
1-butyl-3-methylimidazolium tris (pentafluoroethyl) trifluorophosphate | bmim-FAP |
1-hexyl-3-methylimidazolium bis (trifluoromethylsulfonyl) amide | hmim-NTf2 |
1-octyl-3-methylimidazolium bis (trifluoromethylsulfonyl) amide | omim-NTf2 |
1-octyl-3-methylimidazolium bis (trifluoroethylsulfonyl) amide | omim-BETI |
1-decyl-3-methylimidazolium bis (trifluoromethylsulfonyl) amide | C10mim-NTf2 |
1-butyl-2, 3-dimethylimidazolium bis (trifluoromethylsulfonyl) amide | C4mmim-NTf2 |
1- (2-methoxyethyl) -3-methylimidazolium tris (pentafluoroethyl) trifluorophosphate | MeOEtmim-FAP |
1- (8-hydroxyoctyl) -3-methylimidazolium bis (trifluoromethylsulfonyl) amide | HOC8mim-NTf2 |
3-methylimidazolium bis (trifluoromethylsulfonyl) amide | C8-H4F13mim-NTf2 |
Dimethylaminoethyl-dimethylethylammonium bis (trifluoromethyl) sulfonyl amide | iPr2N(CH2)2mim-NTf2 |
1-butylpyridinium bis (trifluoromethylsulfonyl) amide | bpyr-NTf2 |
1- (2-methoxyethyl) -pyridinium tris (pentafluoroethyl) trifluorophosphate | MeOEtpyr-FAP |
1- (4-cyanobutyl) -3-methylimidazolium bis (trifluoromethylsulfonyl) amide | (4-CN)bmim-NTf2 |
Trimethyl (butyl) ammonium bis (trifluoromethylsulfonyl) amide | N1114-NTf2 |
Trimethyl (octyl) ammonium bis (trifluoromethylsulfonyl) amide | N1118-NTf2 |
1- (2-diisopropylaminoethyl) dimethylethylammonium bis (trifluoromethyl) sulfonylamide | iPr2N(CH2)2N211-NTf2 |
Dimethylaminoethyl-dimethylethylammonium bis (trifluoromethyl) sulfonyl amide | Me2N(CH2)2N211-NTf2 |
Choline bis (trifluoromethylsulfonyl) amide | choline-NTf2 |
1-butyl-1-methylpyrrolidinium bis (trifluoromethylsulfonyl) amide | C4mpyrr-NTf2 |
N-trimethylbetaine bis (trifluoromethylsulfonyl) amide | C1Hbet-NTf2 |
Triethyl (octyl) phosphonium bis (trifluoromethylsulfonyl) amide | P2228-NTf2 |
Trioctyl (methyl) phosphonium bis (trifluoromethylsulfonyl) amide | P8881-NTf2 |
1- (2-diisopropylaminoethyl) trioctylphosphonium bis (trifluoromethyl) sulphonyl amide | iPr2N(CH2)2P888-NTf2 |
Trihexyl (tetradecyl) phosphonium chloride | P666,14-Cl |
Trihexyl (tetradecyl) phosphonium hydroxide | P666,14-OH |
Trihexylphosphonium bis (trifluoromethylsulfonyl) amide | P666,14-NTf2 |
Trihexyl (tetradecyl) phosphonium tris (pentafluoroethyl) trifluorophosphate | P666,14-FAP |
Trihexyl (tetradecyl) phosphonium formate | P666,14-formate |
Trihexyl (tetradecyl) phosphonium acetate | P666,14-OAc |
Trihexyl (tetradecyl) phosphonium isobutyrate | P666,14-isobutyrate |
Trihexyl (tetradecyl) phosphonium hexanoate | P666,14-hexanoate |
Trihexyl (tetradecyl) phosphonium 2-ethylbutanoate | P666,14-2EB |
Trihexyl (tetradecyl) phosphonium 2, 2-dimethylbutyrate | P666,14-2,2-DMB |
Trihexyl (tetradecyl) phosphonium octanoates | P666,14-octanoate |
Trihexyl (tetradecyl) phosphonium 2-ethylhexanoate | P666,14-2EH |
Trihexyl (tetradecyl) phosphonium dodecanoate | P666,14-dodecanoate |
Trihexyl (tetradecyl) phosphonium succinate | P666,14-succinate |
Example 1
666,14Synthesis of P-OH
Will P666,14-Cl (81.70 g, 157.32 mmol) was dissolved in methanol (19.78 g, 617.35 mmol) and the solution was settled down for further ion exchange reaction. Using ion exchange resin (170 cm)3Amberlite IRN-78) packed column and the resin washed with methanol. Then the P is added666,14The Cl solution was slowly added to the column, and the flow rate was controlled at 1 drop/2 sec. Thereafter, methanol (80 mL, 1977.03 mmol) was slowly added to the column to add all P666,14OH was washed out into a 500 mL single-necked round bottom flask. All P contained in the column was collected666,14After the solution of-OH, 5 drops of the solution were mixed with 3 drops of HNO3And 3 drops of AgNO3Mixed to test whether all halogen ions have been exchanged. This procedure is repeated as necessary.
In solution of P666,14Concentration of-OH1H NMR analysis, and P in methanol666,14The weight% of-OH is determined by the relative integral of acidic proton to the hydrocarbon chain of methyl versus phosphonium salt of methanol.
Example 2
666,14Synthesis of P-2EH
P in methanol determined in example 1666,14Calculated weight fraction of-OH (P)666,14Weight fraction of OH = 0.3032), the neutralization P is calculated as follows666,14-acids required for OH:
MW = 144.21 for 2-EH Acid;
P666,14MW = 500.86 for OH;
weight of desired 2-EH Acid = { [ (weight of hydroxide MeOH solution) ((P))666,14Weight% of-OH] / (P666,14MW of-OH) } { (MW of 2-EH Acid) = { [ (252.36 g) } [0.3032/(500.86 g/mol)]} * (144.12 g/mol) = 22.017 g。
2-Ethylhexanoic acid (22.04 g, 152.93 mmol) was added to the P666,14-OH solution, then the solution was stirred for 6 hours. Then rotate onThe solution was dried in a rotary evaporator at 40 ℃ for 6 hours. Further drying was carried out in a high vacuum drying system for 6 hours. The formed carboxylate salt is then ready for liquid-liquid extraction (LLE) experiments and further characterization, such as moisture content measurement, differential scanning calorimetry, thermogravimetric analysis, and elemental analysis.
The figure shows P at 300 MHz666,14-2EH in CDCl3In (1)1H NMR spectrum.
Example 3
Acetic acid extraction using representative NIO solvents
The tie line data at high (typically about 16-20 wt% HOAc in the organic phase) and low acetic acid concentrations (typically about 1-5 wt% HOAc in the organic phase) were measured for each solvent at the temperatures given in table 3.
Approximately equal masses of water and solvent were added to the glass vials. Acetic acid was added to the solvent-water mixture in an amount sufficient to generate high or low acid concentration data. Once acetic acid was added, the mixture was stirred vigorously and then allowed to separate into a clear phase while maintaining the specified temperature. The phases were sampled and analyzed by gas chromatography for water and acetic acid wt%. These data are used to calculate the distribution coefficient and control the distribution coefficient PcontIs considered to be the smaller of the partition coefficients at high and low acid concentrations. This data was also used to calculate the water/acetic acid weight ratio R at high acid concentrationsextr. The results are shown in Table 3.
TABLE 3
Acetic acid extraction factor of non-ionic organic solvents
Solvent(s) | T (℃) | Pcont | At PcontHOAc (wt%) of | Rextr | Extraction factor (epsilon) |
EtOAc | 25 | 0.99 | 1.5 | 0.98 | 1.01 |
n-BuOAc | 40 | 0.41 | 1.6 | 0.52 | 0.79 |
nPrOAc | 40 | 0.51 | 2.2 | 0.70 | 0.73 |
iPrOAc | 40 | 0.54 | 1.8 | 0.65 | 0.83 |
| 20 | 2.85 | 17.0 | 0.7 | 4.07 |
2EH Acid | 40 | 0.32 | 1.3 | 0.29 | 1.10 |
MTBE | 40 | 0.7 | 2.0 | 0.5 | 1.40 |
TAME | 40 | 0.42 | 1.5 | 0.34 | 1.24 |
2-hexanones a | 35 | 0.91 | 3.9 | 0.97 | 0.93 |
MIBK | 35 | 0.65 | 1.6 | 0.53 | 1.23 |
MAK | 40 | 0.49 | 1.7 | 0.41 | 1.20 |
MIAK | 40 | 0.46 | 1.7 | 0.34 | 1.35 |
DPK | 40 | 0.32 | 1.3 | 0.31 | 1.03 |
Isophorone | 40 | 1.1 | 1.2 | 0.67 | 1.64 |
a Data is taken fromJ. Chem. Eng. Data, 46, 2001, 1450-56。
Although PrCN has a relatively high extraction factor, it has the same boiling point as acetic acid, forms an azeotrope with acetic acid, and is therefore very difficult to separate from acetic acid.
Example 4
Acetic acid extraction using phosphate ester solvents
The tie-line data at high (typically about 15-20 wt% HOAc in the organic phase) and low acetic acid concentrations (typically about 1-2 wt% HOAc in the organic phase) were measured for each solvent (either the pure phosphate or a mixture of phosphate and NIO solvent) at the temperatures given in table 4.
Approximately equal masses of water and solvent were added to the glass vials. Acetic acid was added to the solvent-water mixture in an amount sufficient to generate high or low acid concentration data. Once acetic acid was added, the mixture was stirred vigorously and then allowed to separate into a clear phase while maintaining the specified temperature. The phases were sampled and analyzed by gas chromatography for water and acetic acid wt%. These data are used to calculate the distribution coefficient and control the distribution coefficient PcontIs considered to be the smaller of the partition coefficients at high and low acid concentrations. This data was also used to calculate the water/acetic acid weight ratio R at high acid concentrationsextr. The results are shown in Table 4.
TABLE 4
Acetic acid extraction of phosphate ester-containing compositions at 40 deg.C
Solvent(s) | Pcont | At PcontHOAc (wt%) of | Rextr | Extraction factor (epsilon) |
Phosphoric acid tributyl ester | 0.78 | 18.1 | 0.39 | 2.00 |
25 wt% TBP, 75 wt% MTBE | 0.94 | 19.7 | 0.52 | 1.81 |
25 wt% TBP, 75 wt% iPrOAc | 0.80 | 18.1 | 0.61 | 1.31 |
Triethyl phosphate | 0.33 | 16.2 | 0.12 | 2.75 |
25 wt.% TEHP, 75 wt.% MTBE | 0.71 | 16.9 | 0.30 | 2.37 |
25 wt.% TEHP, 75 wt.% iPrOAc | 0.62 | 15.8 | 0.39 | 1.59 |
Such as those manufactured by Wardell and King ("Solvent Equilibria for Extraction of Carboxylic Acids from Water"J. Chem. and Eng. DataVol 23, number 2, pp 144-148 (1978)) expected that the extraction factor of phosphate solvents was slightly improved compared to those of NIO solvents.
Example 5
Acetic acid extraction using Cyanex 923
The tie-line data at high (typically about 15-20 wt% HOAc in the organic phase) and low acetic acid concentration (typically about 1-2 wt% HOAc in the organic phase) were measured for each solvent (commercially available Cyanex 923 or mixtures of Cyanex 923 and non-ionic organic solvents) at the temperatures given in table 5.
Approximately equal masses of water and solvent were added to the glass vials. Acetic acid was added to the solvent-water mixture in an amount sufficient to generate high or low acid concentration data. Once acetic acid was added, the mixture was stirred vigorously and then allowed to separate into a clear phase while maintaining the specified temperature. The phases were sampled and analyzed by gas chromatography for water and acetic acid wt%. These data are used to calculate the distribution coefficient and control the distribution coefficient PcontIs considered to be the smaller of the partition coefficients at high and low acid concentrations. This data was also used to calculate the water/acetic acid weight ratio R at high acid concentrationsextr. KnotThe results are listed in table 5.
TABLE 5
Acetic acid extraction factor at 40 ℃ for Cyanex-containing compositions
Solvent(s) | Pcont | At PcontHOAc (wt%) of | Rextr | Extraction factor (epsilon) |
Cyanex 923 | 0.94 | 19.0 | 0.26 | 3.62 |
75 wt% MTBE/25 wt% C923 | 0.89 | 20.0 | 0.36 | 2.47 |
75 wt% iPrOAc/25 wt% C923 | 0.77 | 20.0 | 0.43 | 1.79 |
Example 6
Acetic acid extraction using hydrophobic liquid salts
The tie line data at high (typically about 7-25 wt% HOAc in the organic phase) and low acetic acid concentrations (typically about 0.2 to 5 wt% HOAc in the organic phase) were measured for each solvent at the temperatures specified in table 6.
Some solvents exhibit very low acid partition coefficients, and the two-phase region does not extend much above about 7 wt% acetic acid. Equilibrium data for each compound was measured in the following manner.
3 g of solvent were pipetted into a jacketed glass tankTo this was added 3 grams of an aqueous mixture of acetic acid (prepared to generate high or low acid concentration data). A stir bar was introduced into the vial and the contents were sealed with a plastic cap and a layer of sealing film tape. The cell is maintained at the desired temperature by means of a constant temperature fluid circulated through the jacket of the cell. The mixture was stirred vigorously for 1.5 hours and then allowed to separate into a clear phase without stirring while maintaining the specified temperature. After 6 hours settling time, the phases were sampled and analyzed by NMR for water and acetic acid wt%. These data are used to calculate the distribution coefficient and control the distribution coefficient PcontIs considered to be the smaller of the partition coefficients at high and low acid concentrations. This data was also used to calculate the water/acetic acid weight ratio R at high acid concentrationsextr. The results are shown in Table 6.
TABLE 6
Extraction of acetic acid in a series of hydrophobic solvents at 20 deg.C
Solvent(s) | Pcont | At PcontHOAc (wt%) of | Rextr | Extraction factor (epsilon) |
emim-NTf2 | 0.30 | 7.1 | 0.85 | 0.35 |
bmim-NTf2 | 0.21 | 1.4 | 0.69 | 0.31 |
bmim-NTf2 b | 0.24 | 5.4 | 0.79 | 0.30 |
bmim-FAP | 0.00 | 1.5 | 0.17 | 0.00 |
bmim-FAPb | 0.06 | 1.7 | 0.33 | 0.18 |
bmim-BETI | 0.06 | 0.6 | 0.39 | 0.15 |
hmim-NTf2 | 0.19 | 4.6 | 0.56 | 0.34 |
omim-NTf2 | 0.18 | 0.9 | 0.47 | 0.38 |
omim-NTf2 a | 0.12 | 11.8 | 0.68 | 0.17 |
omim-BETI | 0.05 | 0.5 | 0.50 | 0.11 |
C10mim-NTf2 | 0.13 | 3.6 | 0.39 | 0.34 |
C4mmim-NTf2 | 0.13 | 1.1 | 0.59 | 0.22 |
iPr2N(CH2)2mim-NTf2 | 0.18 | 4.5 | 0.88 | 0.20 |
MeOEtmim-FAP | 0.04 | 0.3 | 0.23 | 0.15 |
4CNbmim-NTf2 | 0.65 | 11.0 | 0.82 | 0.79 |
HOC8mim-NTf2 | 0.54 | 7.6 | 0.98 | 0.55 |
(C6F13)-(C2H4)mim-NTf2 | 0.08 | 0.7 | 0.60 | 0.13 |
C4mpyrr-NTf2 | 0.33 | 9.5 | 0.45 | 0.74 |
bpyr-NTf2 | 0.22 | 5.1 | 0.69 | 0.31 |
MeOEtpyr-FAP | 0.06 | 0.2 | 0.23 | 0.26 |
N1114-NTf2 | 0.13 | 1.9 | 0.84 | 0.16 |
N1118-NTf2 | 0.06 | 1.2 | 0.47 | 0.14 |
Me2N(CH2)2N211-NTf2 | 0.53 | 9.5 | 2.00 | 0.26 |
iPr2N(CH2)2N211-NTf2 | 0.14 | 4.0 | 0.77 | 0.19 |
choline-NTf2 | 0.82 | 14.0 | 1.64 | 0.50 |
C1Hbet-NTf2 | 0.76 | 12.7 | 1.48 | 0.51 |
P2228-NTf2 b | 0.10 | 2.8 | 0.33 | 0.30 |
P4444-2EH | 0.52 | 7.3 | 1.452 | 0.36 |
P8881-NTf2 | 0.05 | 0.8 | 0.43 | 0.13 |
iPr2N(CH2)2P888-NTf2 | 0.21 | 5.4 | 0.74 | 0.28 |
P666,14-Cl | 0.38 | 8.5 | 0.63 | 0.60 |
P666,14-NTf2 | 0.06 | 1.8 | 0.88 | 0.07 |
P666,14-FAP | 0.02 | 0.1 | 0.23 | 0.10 |
a Equilibrating at 75 ℃ instead of 20 ℃
b Data were taken from Hashikawa, JP appl. Kokai 2014/40389.
Example 7
Acetic acid extraction using tetraalkyl phosphonium carboxylates
The tie line data at high (typically about 9-21 wt% HOAc in the organic phase) and low acetic acid concentrations (typically about 0.2 to 5 wt% HOAc in the organic phase) were measured at 20 ℃ for each of the solvents listed in table 7.
Approximately equal masses of water and solvent were added to the glass vials. All extraction solvents contained essentially 100 mole% of the carboxylic acid salt. Acetic acid was added to the solvent-water mixture in an amount sufficient to generate high or low acid concentration data. Once acetic acid was added, the mixture was stirred vigorously and then allowed to separate into a clear phase while maintaining the specified temperature. The phases were sampled and analyzed by NMR for water and acetic acid wt%. These data are used to calculate the distribution coefficient and control the distribution coefficient PcontIs considered to be the smaller of the partition coefficients at high and low acid concentrations. This data was also used to calculate the water/acetic acid weight ratio R at high acid concentrationsextr. The results are shown in Table 7.
TABLE 7
Extraction of different phosphonium carboxylates with acetic acid at 20 deg.C
Solvent(s) | Pcont | At PcontHOAc (wt%) of | Rextr | Extraction factor (epsilon) |
P666,14-formate salt | 2.47 | 19.7 | 0.28 | 8.73 |
P666,14-acetate salt | 4.98 | 9.1 | 1.08 | 4.59 |
P666,14-hexanoic acid salt | 3.32 | 20.3 | 0.25 | 13.48 |
P666,14-2EB | 2.15 | 21.6 | 0.24 | 8.91 |
P666,14-2,2-DMB | 2.41 | 20.3 | 0.29 | 8.32 |
P666,14-octanoic acid salts | 3.17 | 19.9 | 0.24 | 12.99 |
P666,14-2EH | 3.24 | 20.4 | 0.21 | 15.21 |
P666,14Dodecyl sulfate salt | 2.62 | 20.2 | 0.23 | 11.17 |
P666,14-succinic acid salt | 4.72 | 11.9 | 0.58 | 8.07 |
Example 8
666,14 1 4C to C carboxylic acid extraction using P-2EH
The bond line data at high (typically about 16-25 wt% lower acid in the organic phase) and low acid concentrations (typically about 0.2 to 5 wt% in the organic phase) were measured at 20 ℃ for each of the acids listed in table 8.
Approximately equal masses of water and solvent were added to the glass vials. All extraction solvents contained essentially 100 mole% of the carboxylic acid salt. Acid is added to the solvent-water mixture in an amount sufficient to generate high or low acid concentration data. Upon addition of the lower acid, the mixture was stirred vigorously and then allowed to separate into a clear phase while maintaining the specified temperature. The phases were sampled and analyzed by NMR for water and lower acid wt%. These data are used to calculate the distribution coefficient and control the distribution coefficient PcontIs considered to be the smaller of the partition coefficients at high and low acid concentrations. This data was also used to calculate the water/acid weight ratio R at high acid concentrationsextr. The results are shown in Table 8.
TABLE 8
Multiple carboxylic acid extraction of P666,14-2EH
Hyaluronic acid | Pcont | At PcontCarboxylic acid of (b)% by weight | Rextr | Extraction factor (epsilon) |
Formic acid | 1.35 | 16.5 | 0.19 | 7.03 |
Acetic acid | 3.24 | 20.4 | 0.21 | 15.21 |
Propionic acid | 7.64 | 25.1 | 0.16 | 47.28 |
N-butyric acid | 4.64 | 22.0 | 0.17 | 27.05 |
Acrylic acid | 4.77 | 20.9 | 0.16 | 28.49 |
Example 9
666,14Acetic acid extraction using P-2EH and/or NIO co-solvents
The tie line data at high (typically about 20-25 wt% HOAc in the organic phase) and low acetic acid concentrations (typically about 0.2 to 5 wt% HOAc in the organic phase) are measured at 20 ℃ for each of the solvents listed in table 9.
Approximately equal masses of water and extraction solvent containing varying amounts of carboxylate and NIO solvent were added to the glass vials. N-hexanoic acid and 2-ethylhexanoic acid (2-EH acid) were tested as NIO solvents. Acetic acid was added to the solvent-water mixture in an amount sufficient to generate high or low acid concentration data. Once acetic acid was added, the mixture was stirred vigorously and then allowed to separate into a clear phase while maintaining the specified temperature. Taking each phaseSamples were analyzed by NMR for water and acetic acid (wt%). These data are used to calculate the distribution coefficient and control the distribution coefficient PcontIs considered to be the smaller of the partition coefficients at high and low acid concentrations. This data was also used to calculate the water/acetic acid weight ratio R at high acid concentrationsextr. The results are shown in Table 9.
The results of the extractions with 2-EH acid alone and n-hexanoic acid alone are included in Table 9 for comparison.
TABLE 9
Effect of NIO solvent identity and concentration on acetic acid extraction
Carboxylate solvents | NIO solvent | Pcont | At PcontHOAc (wt%) of | Rextr | Extraction factor (epsilon) |
Is free of | 100 mol% 2-EH acid a | 0.32 | 0.32 | 0.29 | 1.10 |
Is free of | 100 mol% of n-hexanoic acid | 0.56 | 1.8 | 1.07 | 0.53 |
P666,14-2EH | Is free of | 3.24 | 20.4 | 0.21 | 15.21 |
P666,14-2EH | 10 mol% 2-EH acid | 2.19 | 21.7 | 0.21 | 10.40 |
P666,14-2EH | 30 mol% 2-EH acid | 1.80 | 19.7 | 0.22 | 8.18 |
P666,14-2EH | 50 mol% 2-EH acid | 0.86 | 23.9 | 0.22 | 3.87 |
P666,14-2EH | 80 mol% 2-EH acid | 0.53 | 25.8 | 0.30 | 1.79 |
P666,14-2EH | 90 mol% 2-EH acid | 0.48 | 25.0 | 0.46 | 1.05 |
P666,14-2EH | 10 mol% of n-hexanoic acid | 2.26 | 20.9 | 0.22 | 10.03 |
P666,14- | 20 mol% of n-hexanoic acid | 1.97 | 20.5 | 0.22 | 8.73 |
P666,14-2EH | 30 mol% of n-hexanoic acid | 2.00 | 19.6 | 0.24 | 8.31 |
P666,14-2EH | 50 mol% of n-hexanoic acid | 1.15 | 20.5 | 0.27 | 4.21 |
a Equilibration at 40 ℃.
Example 10
666,14Acetic acid extraction using P-hexanoic acid salt and/or n-hexanoic acid
The tie line data at high (typically about 20 wt% HOAc in the organic phase) and low acetic acid concentrations (typically about 0.2 to 5 wt% HOAc in the organic phase) were measured at 20 ℃ for each of the solvents listed in table 10.
Approximately equal masses of water and extraction solvent containing varying amounts of carboxylate and NIO solvent were added to the glass vials. N-hexanoic acid was tested as the NIO solvent. Acetic acid was added to the solvent-water mixture in an amount sufficient to generate high or low acid concentration data. Once acetic acid was added, the mixture was stirred vigorously and then allowed to separate into a clear phase while maintaining the specified temperature. The phases were sampled and analyzed by NMR for water and acetic acid wt%. These data are used to calculate the distribution coefficient and control the distribution coefficient PcontIs considered to be the smaller of the partition coefficients at high and low acid concentrations. This data was also used to calculate the water/acetic acid weight ratio R at high acid concentrationsextr. The results are shown in Table 10.
The results of the extraction with n-hexanoic acid alone are included in table 10 for comparison.
Watch 10
Effect of n-hexanoic acid on acetic acid extraction of P666, 14-hexanoic acid salt
Of n-hexanoic acidAmount (mol%) | Pcont | At PcontHOAc (wt%) of | Rextr | Extraction factor (epsilon) |
Is free of | 3.32 | 20.3 | 0.25 | 13.48 |
30 | 2.97 | 19.3 | 0.26 | 11.36 |
50 | 1.80 | 19.6 | 0.27 | 6.63 |
70 | 1.15 | 15.4 | 0.43 | 2.69 |
90 | 0.65 | 14.7 | 0.86 | 0.76 |
95 | 0.68 | 14.3 | 1.19 | 0.57 |
100 | 0.56 | 1.8 | 1.07 | 0.53 |
Example 11
666,14Acetic Acid extraction using P-2EB and/or 2-EB Acid
The tie line data at high (typically about 14-20 wt% HOAc in the organic phase) and low acetic acid concentrations (typically about 0.2 to 5 wt% HOAc in the organic phase) are measured at 20 ℃ for each of the solvents listed in table 11.
Approximately equal masses of water and extraction solvent containing varying amounts of carboxylate and NIO solvent were added to the glass vials. 2-Ethylbutyric acid was tested as a NIO solvent. Acetic acid was added to the solvent-water mixture in an amount sufficient to generate high or low acid concentration data. Once acetic acid was added, the mixture was stirred vigorously and then allowed to separate into a clear phase while maintaining the specified temperature. The phases were sampled and analyzed by NMR for water and acetic acid wt%. These data are used to calculate the distribution coefficient and control the distribution coefficient PcontIs considered to be the smaller of the partition coefficients at high and low acid concentrations. This data was also used to calculate the water/acetic acid weight ratio R at high acid concentrationsextr. The results are shown in Table 11.
TABLE 11
Effect of 2-EB Acid on acetic Acid extraction of P666,14-2EB
Amount of 2EB Acid (mol%) | Pcont | At PcontHOAc (wt%) of | Rextr | Extraction factor (epsilon) |
Is free of | 2.15 | 21.6 | 0.24 | 8.91 |
10 | 4.75 | 20.7 | 0.24 | 19.80 |
30 | 2.76 | 22.6 | 0.26 | 10.58 |
50 | 2.05 | 19.9 | 0.29 | 7.05 |
70 | 1.59 | 14.4 | 0.50 | 3.18 |
80 | 1.01 | 14.4 | 0.63 | 1.61 |
90 | 1.01 | 14.2 | 0.85 | 1.19 |
95 | 0.82 | 14.2 | 1.10 | 0.74 |
Example 12
666,14Acetic acid extraction using P-isobutyrate and i-HOBu
The tie line data at high (typically about 20 wt% HOAc in the organic phase) and low acetic acid concentrations (typically about 0.2 to 5 wt% HOAc in the organic phase) were measured at 20 ℃ for each of the solvents listed in table 12.
Approximately equal masses of water and extraction solvent containing varying amounts of carboxylate and NIO solvent were added to the glass vials. Isobutyric acid was tested as the NIO solvent. Acetic acid was added to the solvent-water mixture in an amount sufficient to generate high or low acid concentration data. Once acetic acid was added, the mixture was stirred vigorously and then allowed to separate into a clear phase while maintaining the specified temperature. The phases were sampled and analyzed by NMR for water and acetic acid wt%. These data are used to calculate the distribution coefficient and control the distribution coefficient PcontIs considered to be the smaller of the partition coefficients at high and low acid concentrations. This data was also used to calculate the water/acetic acid weight ratio R at high acid concentrationsextr. The results are shown in Table 12 in (c).
TABLE 12
Effect of isobutyric acid on acetic acid extraction of P666, 14-isobutyrate
Amount of isobutyric acid (mol%) | Pcont | At PcontHOAc (wt%) of | Rextr | Extraction factor (epsilon) |
10 | 3.19 | 19.3 | 0.273 | 11.69 |
30 | 2.08 | 20.6 | 0.255 | 8.16 |
50 | 1.67 | 18.8 | 0.275 | 6.08 |
Example 13
666,14Acetic acid extraction using P-n-octanoate and/or n-octanoic acid
The tie line data at high (typically about 20-25 wt% HOAc in the organic phase) and low acetic acid concentrations (typically about 0.2 to 5 wt% HOAc in the organic phase) are measured at 20 ℃ for each of the solvents listed in table 13.
Approximately equal masses of water and extraction solvent containing varying amounts of carboxylate and NIO solvent were added to the glass vials. N-octanoic acid was tested as the NIO solvent. Acetic acid was added to the solvent-water mixture in an amount sufficient to generate high or low acid concentration data. Once added toAcetic acid, the mixture was stirred vigorously and then allowed to separate into a clear phase while maintaining the specified temperature. The phases were sampled and analyzed by NMR for water and acetic acid wt%. These data are used to calculate the distribution coefficient and control the distribution coefficient PcontIs considered to be the smaller of the partition coefficients at high and low acid concentrations. This data was also used to calculate the water/acetic acid weight ratio R at high acid concentrationsextr. The results are shown in Table 13.
Watch 13
Effect of caprylic acid on acetic acid extraction of P666, 14-caprylate
Amount of octanoic acid (% by mol) | Pcont | At PcontHOAc (wt%) of | Rextr | Extraction factor (epsilon) |
Is free of | 3.17 | 19.9 | 0.24 | 12.99 |
50 | 1.03 | 25.7 | 0.21 | 4.76 |
Example 14
Effect of temperature on extraction Using NIO solvent
The tie line data was measured at 22 and 40 ℃ for each of the solvents listed in table 14.
Approximately equal masses of water and solvent were added to the glass vials. Acetic acid was added to the solvent-water mixture in an amount sufficient to generate high or low acid concentration data. Once acetic acid was added, the mixture was stirred vigorously, followed by maintaining the specificationsThe temperature was simultaneously allowed to separate into a clear phase. The phases were sampled and analyzed by gas chromatography for water and acetic acid wt%. These data are used to calculate the distribution coefficient and control the distribution coefficient PcontIs considered to be the smaller of the partition coefficients at high and low acid concentrations. The results are shown in Table 14.
TABLE 14
Effect of temperature on acetic acid partitioning in NIO solvent
Solvent(s) | T (℃) | Pcont | At PcontHOAc (wt%) of | Rextr | Extraction factor (epsilon) |
MTBE | 22 | 0.86 | 2.0 | 0.46 | 1.88 |
MTBE | 40 | 0.70 | 2.0 | 0.50 | 1.40 |
MIBK | 22 | 0.67 | 3.9 | 1.14 | 0.59 |
MIBK | 40 | 0.75 | 8.4 | 0.73 | 1.02 |
i-PrOAc | 22 | 0.57 | 1.7 | 0.56 | 1.02 |
i-PrOAc | 40 | 0.54 | 1.8 | 0.65 | 0.83 |
As seen from table 14, the partition coefficient and extraction factor respond differently to temperature changes in different NIO solvents.
Example 15
666,14Effect of temperature on acetic acid extraction Using P-carboxylates
The tie line data was measured at 20 and 75 ℃ for each of the solvents listed in table 15.
Approximately equal masses of water and solvent were added to the glass vials. Acetic acid was added to the solvent-water mixture in an amount sufficient to generate high or low acid concentration data. Once acetic acid was added, the mixture was stirred vigorously and then allowed to separate into a clear phase while maintaining the specified temperature. The phases were sampled and analyzed by gas chromatography for water and acetic acid wt%. These data are used to calculate the distribution coefficient and control the distribution coefficient PcontIs considered to be the smaller of the partition coefficients at high and low acid concentrations. The results are shown in Table 15.
Watch 15
Effect of temperature on acetic acid extraction of P666, 14-Carboxylic acid salts
Carboxylate solvents | NIO solvent | T (℃) | Pcont | At PcontHOAc (wt%) of | Rextr | Extraction factor (epsilon) |
P666,14-2EH | Is free of | 20 | 3.24 | 20.4 | 0.21 | 15.21 |
P666,14-2EH | Is free of | 75 | 1.86 | 20.2 | 0.24 | 7.59 |
P666,14-hexanoic acid salt | Is free of | 20 | 3.32 | 20.3 | 0.25 | 13.48 |
P666,14-hexanoic acid salt | Is free of | 75 | 1.89 | 21.0 | 0.12 | 16.15 |
P666,14-hexanoic acid salt | 10 mol% hexanoic acid | 75 | 2.14 | 21.5 | 0.24 | 8.91 |
P666,14-2EB | Is free of | 20 | 2.15 | 21.6 | 0.24 | 8.91 |
P666,14-2EB | Is free of | 75 | 1.87 | 20.9 | 0.27 | 6.94 |
P666,14-2EB | 10 mol% 2-EB acid | 75 | 2.24 | 20.0 | 0.26 | 8.63 |
As with the NIO solvents (see table 14), both the partition coefficient and the extraction factor increased and decreased with respect to temperature in different phosphonium carboxylate solvents (see table 15). Notably, in some cases, the extraction factor increases with increasing temperature.
Procedures of examples 16 to 19
Three NIO solvents (MIBK, MTBE, and n-butyl acetate) and a carboxylate solvent P were used666,14-2EH measurement of the bond line data for the extraction of lower carboxylic acids (formic, propionic, n-butyric and acrylic acids) from water.
The bond line data at high (typically about 10-25 wt% carboxylic acid in the organic phase) and low acid concentrations (typically about 1 to 5 wt% acid in the organic phase) were measured for each solvent at 40 ℃.
Approximately equal masses of water and solvent were added to the glass vials. The desired amount of carboxylic acid is added to the solvent-water mixture in an amount sufficient to generate data for high or low acid concentrations. Once the acid was added, the mixture was stirred vigorously and then allowed to separate into a clear phase while maintaining the specified temperature. The phases were sampled and analyzed by gas chromatography for water and carboxylic acid wt%. These data are used to calculate the distribution coefficient and control the distribution coefficient PcontIs considered to be the smaller of the partition coefficients at high and low acid concentrations. This data is also used to calculate the water/carboxylic acid weight ratio R at high acid concentrationsextr。
Example 16
666,14Formic acid extraction with NIO solvent compared to P-2EHGet
This example presents the use of NIO solvents (MTBE, MIBK and n-butyl acetate) and P according to the extraction procedure described above666,14-2 extraction factor of EH extraction of formic acid. The results are shown in Table 16.
TABLE 16
Partitioning of the NIO solvent with formic acid in P666,14-2EH (40 ℃ C.)
Solvent(s) | Pcont | At PcontHOAc (wt%) of | Rextr | Extraction factor (epsilon) |
MTBE | 0.7 | 16.8 | 0.69 | 1.0 |
MIBK | 0.6 | 14.3 | 0.74 | 0.8 |
BuOAc | 0.4 | 10.0 | 0.58 | 0.6 |
P666,14-2EH | 1.35 | 16.5 | 0.191 | 7.0 |
Example 17
666,14Propionic acid extraction with NIO solvent compared to P-2EH
This example presents the use of NIO solvents (MTBE, MIBK and acetic acid) according to the extraction procedure described aboveN-butyl ester) and P666,14-2 extraction factor for EH extraction of propionic acid. The results are shown in Table 17.
TABLE 17
Partition of the NIO solvent with propionic acid in P666,14-2EH (40 ℃ C.)
Solvent(s) | Pcont | At PcontPropionic acid (wt%) | Rextr | Extraction factor (epsilon) |
MTBE | 3.2 | 20.2 | 0.30 | 10.7 |
MIBK | 2.6 | 18.8 | 0.46 | 5.5 |
BuOAc | 2.0 | 17.7 | 0.30 | 6.50 |
P666,14-2EH | 7.64 | 25.1 | 0.16 | 47.3 |
Example 18
666,14N-butyric acid extraction with NIO solvent compared to P-2EH
This example presents the use of NIO solvents (MTBE, MIBK and n-butyl acetate) and P according to the extraction procedure described above666,14-2 extraction factor for EH extraction of n-butyric acid. The results are shown in Table 18.
Watch 18
Partition of the NIO solvent with n-butyric acid in P666,14-2EH (40 ℃ C.)
Solvent(s) | Pcont | At PcontButyric acid (wt%) | Rextr | Extraction factor (epsilon) |
MTBE | 9.9 | 25.2 | 0.20 | 48.5 |
MIBK | 8.4 | 23.0 | 0.31 | 27.3 |
BuOAc | 6.8 | 22.1 | 0.22 | 30.9 |
P666,14-2EH | 4.6 | 22.0 | 0.17 | 27.0 |
Example 19
666,14Acrylic acid extraction with NIO solvent compared to P-2EH
This example presents the use of NIO solvents (MTBE, MIBK and n-butyl acetate) and P according to the extraction procedure described above666,14-2EH extraction factor for acrylic acid. The results are shown in Table 19.
Watch 19
NIO solvent and acrylic partitioning in P666,14-2EH (40 ℃ C.)
Solvent(s) | Pcont | At PcontAcrylic acid (wt%) of | Rextr | Extraction factor (epsilon) |
MTBE | 3.6 | 24.2 | 0.31 | 11.8 |
MIBK | 2.7 | 21.6 | 1.40 | 6.8 |
BuOAc | 2.1 | 20.6 | 0.30 | 6.9 |
P666,14-2EH | 4.8 | 20.9 | 0.17 | 28.5 |
The invention has been described in detail with particular reference to preferred embodiments thereof, but it will be understood that variations and modifications can be effected within the spirit and scope of the invention.
Claims (30)
1. For mixing C1To C4A composition for separating carboxylic acid from water, the composition comprising:
(a) a quaternary phosphonium carboxylate;
(b) a hydrophobic non-ionic organic solvent selected from ketones, aromatic hydrocarbons, saturated hydrocarbons, ethers, esters, chlorinated hydrocarbons, nitriles and higher carboxylic acids, wherein the higher carboxylic acids refer to carboxylic acids having 4 to 20 carbon atoms;
(c) C1to C4A carboxylic acid; and
(d) the amount of water is controlled by the amount of water,
wherein the hydrophobic non-ionic organic solvent is not an extract, and
wherein the quaternary phosphonium carboxylate has the general formula 1:
wherein
R1、R2、R3And R4Each independently is C1To C26A hydrocarbon group, provided that R1、R2、R3And R4A total of at least 24 carbon atoms; and is
R5Is hydrogen or C1To C24Non-aromatic hydrocarbon radicals, in which R5Optionally containing alkoxy functionality or halogen functionality.
2. The composition of claim 1, wherein the quaternary phosphonium carboxylate salt comprises a tetraalkylphosphonium salt of formic acid, acetic acid, propionic acid, n-butyric acid, isobutyric acid, n-valeric acid, isovaleric acid, n-hexanoic acid, 2-ethylbutyric acid, heptanoic acid, n-octanoic acid, 2-ethylhexanoic acid, nonanoic acid, decanoic acid, dodecanoic acid, palmitic acid, stearic acid, oleic acid, linolenic acid, mixed plant-derived acids, or chloroacetic acid.
3. The composition of claim 1, wherein the quaternary phosphonium carboxylate salt comprises a trihexyl (tetradecyl) phosphonium salt of formic, acetic, propionic, n-butyric, isobutyric, n-valeric, isovaleric, n-hexanoic, 2-ethylbutyric, heptanoic, n-octanoic, 2-ethylhexanoic, nonanoic, decanoic, dodecanoic, palmitic, stearic, oleic, linolenic, mixed plant-derived or chloroacetic acids.
4. The composition according to claim 1, wherein the quaternary phosphonium carboxylate salt comprises trihexyl (tetradecyl) phosphonium carboxylate.
5. A composition according to claim 1 comprising at least two quaternary phosphonium carboxylates.
6. The composition according to claim 1, wherein the hydrophobic non-ionic organic solvent is selected from the group consisting of higher carboxylic acids, ethers, esters, ketones, aromatic hydrocarbons, chlorinated hydrocarbons and nitriles.
7. The composition according to claim 6, wherein the hydrophobic non-ionic organic solvent comprises a higher carboxylic acid.
8. The composition of claim 7, wherein the higher carboxylic acid is selected from the group consisting of n-butyric acid, isobutyric acid, n-valeric acid, isovaleric acid, n-hexanoic acid, 2-ethylbutyric acid, heptanoic acid, n-octanoic acid, 2-ethylhexanoic acid, nonanoic acid, decanoic acid, dodecanoic acid, stearic acid, oleic acid, linolenic acid, and mixed plant-derived acids.
9. The composition of claim 8 wherein the higher carboxylic acid is selected from the group consisting of n-butyric acid, isobutyric acid, n-valeric acid, isovaleric acid, n-hexanoic acid, 2-ethylbutyric acid, heptanoic acid, n-octanoic acid, and 2-ethylhexanoic acid.
10. The composition according to claim 1, wherein the hydrophobic non-ionic organic solvent is selected from the group consisting of esters containing 4 to 6 carbon atoms, ketones containing 5 to 9 carbon atoms and ethers containing 4 to 8 carbon atoms.
11. The composition according to claim 1, wherein the hydrophobic non-ionic organic solvent is selected from the group consisting of ethyl acetate, n-propyl formate, isopropyl acetate, isopropyl formate, n-butyl acetate, n-butyl formate, isobutyl acetate, isobutyl formate, n-propyl propionate, isopropyl propionate, 2-pentanone, 3-pentanone, methyl isobutyl ketone, 3-methyl-2-butanone, 2-hexanone, 2-heptanone, cyclohexanone, 4-methyl-2-pentanone, 2, 4-dimethyl-3-pentanone, 5-methyl-2-hexanone, 4-heptanone, 2-octanone, 5-nonanone, 2, 8-dimethyl-4-heptanone, 3, 5-trimethylcyclohexanone, isophorone, Diethyl ether, methyl propyl ether, dipropyl ether, diisopropyl ether, methyl tert-butyl ether, tert-amyl methyl ether, ethyl butyl ether, toluene, m-xylene, p-xylene and o-xylene.
12. The composition according to claim 11, wherein the hydrophobic non-ionic organic solvent is selected from the group consisting of methyl isobutyl ketone, toluene, isopropyl acetate and methyl tert-butyl ether.
13. A composition according to claim 1, comprising at least two hydrophobic non-ionic organic solvents.
14. A composition according to claim 1 comprising 10 to 90% by weight of the quaternary phosphonium carboxylate salt and 10 to 90% by weight of the hydrophobic non-ionic organic solvent.
15. A composition according to claim 1 comprising 50 to 90% by weight of the quaternary phosphonium carboxylate salt and 10 to 50% by weight of the hydrophobic non-ionic organic solvent.
16. A kind of bag C1To C4A process for separating carboxylic acid from water, the process comprising:
make it contain C1To C4A feed mixture of a carboxylic acid and water is contacted with an extraction solvent comprising a quaternary phosphonium carboxylate salt and a hydrophobic nonionic organic solvent in an amount effective to form (a) a composition comprising the quaternary phosphonium carboxylate salt, the hydrophobic nonionic organic solvent, and at least a portion of C from the feed mixture1To C4An extraction mixture of carboxylic acids and (b) a feed mixture comprising water and less C than the feed mixture1To C4A raffinate mixture of carboxylic acids,
wherein the hydrophobic non-ionic organic solvent is not an extract, wherein the hydrophobic non-ionic organic solvent is selected from the group consisting of ketones, aromatic hydrocarbons, saturated hydrocarbons, ethers, esters, chlorinated hydrocarbons, nitriles, and higher carboxylic acids, and wherein the higher carboxylic acid refers to a carboxylic acid having 4 to 20 carbon atoms; and is
Wherein the quaternary phosphonium carboxylate has the general formula 1:
wherein
R1、R2、R3And R4Each independently is C1To C26A hydrocarbon group, provided that R1、R2、R3And R4A total of at least 24 carbon atoms; and is
R5Is C1To C20Non-aromatic hydrocarbon radicals, in which R5Optionally containing alkoxy functionality or halogen functionality.
17. The method of claim 16, wherein the quaternary phosphonium carboxylate salt comprises a tetraalkylphosphonium salt of formic acid, acetic acid, propionic acid, n-butyric acid, isobutyric acid, n-valeric acid, isovaleric acid, n-hexanoic acid, 2-ethylbutyric acid, heptanoic acid, n-octanoic acid, 2-ethylhexanoic acid, nonanoic acid, decanoic acid, dodecanoic acid, palmitic acid, stearic acid, oleic acid, linolenic acid, mixed plant-derived acids, or chloroacetic acid.
18. The method according to claim 16, wherein the quaternary phosphonium carboxylate salt comprises trihexyl (tetradecyl) phosphonium carboxylate.
19. The process according to claim 16, wherein the extraction solvent comprises at least two quaternary phosphonium carboxylates.
20. The process according to claim 16, wherein the hydrophobic non-ionic organic solvent is selected from the group consisting of higher carboxylic acids, ethers, esters, ketones, aromatic hydrocarbons, chlorinated hydrocarbons and nitriles.
21. The process according to claim 20, wherein the higher carboxylic acid is selected from the group consisting of n-butyric acid, isobutyric acid, n-valeric acid, isovaleric acid, n-hexanoic acid, 2-ethylbutyric acid, heptanoic acid, n-octanoic acid, 2-ethylhexanoic acid, nonanoic acid, decanoic acid, dodecanoic acid, stearic acid, oleic acid, linolenic acid, and mixed plant-derived acids.
22. The process according to claim 20, wherein the hydrophobic non-ionic organic solvent is selected from the group consisting of ethyl acetate, n-propyl formate, isopropyl acetate, isopropyl formate, n-butyl acetate, n-butyl formate, isobutyl acetate, isobutyl formate, n-propyl propionate, isopropyl propionate, 2-pentanone, 3-pentanone, methyl isobutyl ketone, 3-methyl-2-butanone, 2-hexanone, 2-heptanone, cyclohexanone, 4-methyl-2-pentanone, 2, 4-dimethyl-3-pentanone, 5-methyl-2-hexanone, 4-heptanone, 2-octanone, 5-nonanone, 2, 8-dimethyl-4-heptanone, 3, 5-trimethylcyclohexanone, isophorone, Diethyl ether, methyl propyl ether, dipropyl ether, diisopropyl ether, methyl tert-butyl ether, tert-amyl methyl ether, ethyl butyl ether, toluene, m-xylene, p-xylene and o-xylene.
23. The method of claim 16, wherein the extraction solvent comprises at least two hydrophobic, nonionic organic solvents.
24. The process according to claim 16, wherein the extraction solvent comprises 10 to 90 wt% of the quaternary phosphonium carboxylate salt and 10 to 90 wt% of the hydrophobic non-ionic organic solvent.
25. The method of claim 16, wherein said C1To C4The carboxylic acid comprises acetic acid.
26. The process according to claim 16, wherein the feed mixture comprises at least two C' s1To C4A carboxylic acid.
27. The process according to claim 16, wherein the feed mixture comprises from 0.5 to 60 wt% of C1To C4A carboxylic acid.
28. The process according to claim 16, wherein said feed mixture is derived from the production of cellulose esters.
29. The process according to claim 16, wherein the weight ratio of the extraction solvent to the feed mixture is from 0.2 to 10: 1.
30. The method of claim 16, further comprising:
separating the extraction mixture from the raffinate mixture; and
recovering C from the extraction mixture by distillation at atmospheric pressure or lower1To C4A carboxylic acid.
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US9616358B2 (en) | 2017-04-11 |
US9573078B2 (en) | 2017-02-21 |
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US20160175737A1 (en) | 2016-06-23 |
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